1048681-67-9Relevant academic research and scientific papers
A Sequential Homologation of Alkynes and Aldehydes for Chain Elongation with Optional 13C-Labeling
Brunner, Andreas,Hintermann, Lukas
, p. 2787 - 2792 (2016/02/27)
Terminal alkynes (RCCH) are homologated by a sequence of ruthenium-catalyzed anti-Markovnikov hydration of alkyne to aldehyde (RCH2CHO), followed by Bestmann-Ohira alkynylation of aldehyde to chain-elongated alkyne (RCH2CCH). Inverting the sequence by starting from aldehyde brings about the reciprocal homologation of aldehydes instead. The use of 13C-labeled Bestmann-Ohira reagent (dimethyl ((1-13C)-1-diazo-2-oxopropyl)phosphonate) for alkynylation provides straightforward access to singly or, through additional homologation, multiply 13C-labeled alkynes. The labeled alkynes serve as synthetic platform for accessing a multitude of specifically 13C-labeled products. Terminal alkynes with one or two 13C-labels in the alkyne unit have been submitted to alkyne-azide click reactions; the copper-catalyzed version (CuAAC) was found to display a regioselectivity of >50 000:1 for the 1,4- over the 1,5-triazine isomer, as shown analytically by 13C NMR spectroscopy.
Finding the proton in a key intermediate of anti-markovnikov alkyne hydration by a bifunctional catalyst
Grotjahn, Douglas B.,Kragulj, Elijah J.,Zeinalipour-Yazdi, Constantinos D.,Miranda-Soto, Valentin,Lev, Daniel A.,Cooksy, Andrew L.
supporting information; experimental part, p. 10860 - 10861 (2009/02/05)
The secondary structure of a bifunctional catalyst positions a crucial reactive proton in the final intermediate of anti-Markovnikov alkyne hydration to give an aldehyde. NMR coupling and isotopic labeling studies elucidate the location of this proton and its involvement in hydrogen bonding. Copyright
